Bisphosphoramide-sulfur compound containing lubricant

ABSTRACT

A lubricating composition is disclosed having improved multifunctional properties and comprises a major amount of an oil of lubricating viscosity and minor amounts of an oleophilic organic sulfur compound containing from 3 to 40 weight percent sulfur and a bisphosphoramide having from 30 to 300 carbon atoms.

United States Patent 1191 Hotten *Jan. 7, 1975 [5BISPHOSPHORAMIDE-SULFUR 2,574,516 11/1951 Walteret a1. 252/49.8 xCOMPOUND CONTAINING LUBRICANT 2,722,518 ll/1955 Watson 252/46.72,736,707 2/1956 Morris 1 252/467 Inventor: ce W-H0tten.0r1nda.Cal1f.3,071,548 1/1963 01611116161. ..252/46.6 3,174,931 3/1965 Matson 61al.... 252/46.7 x [73] Assgnee' g l" f i cmpanyi 3,239,464 3/1966 Matsoner a1. 252/46.6 ranclsco, 3,476,685 11/1969 01561611661 et al 252/46.7 11 Notice: The portion of the term of this 3,705,211 12/1972 Addor etal 1. 260/926 patent subsequent to Jan. 15, 1974, has been di l i dPrimary Examiner-W. Cannon Attorney, Age/mar Firm-G. F. Magdeburger; C.J. [22] F1led. Nov. 17, 1972 Tonkin; D Nelson [21] Appl. No.: 307,732

[57] ABSTRACT [52] U.S.Cl. 252/42.7, 252/46.7, 260/551 P A u i ating ompsiti n is disclosed having im [51] Int. Cl ..C10m1/48 pr d ultifun tinal properties and c mprises a [5 1 F e d of Search 260/551 P; 252/49.9,46.6, major amount of an oil of lubricating viscosity and 2513/46], 42,7minor amounts of an oleophilic organic sulfur compound containing from 3to 40 weight percent sulfur [56] References Cit d and a bisphosphoramidehaving from 30 to 300 car- UNITED STATES PATENTS atoms- 2.146,584 2/1939Lipkin 252/49.8 11 Claims, N0 Drawings BISPHOSPHORAMIDE-SULFUR COMPOUNDCONTAINING LUBRICANT BACKGROUND OF THE INVENTION This invention relatesto an improved lubricating composition. More particularly, thisinvention relates to a lubricating composition containing an additivecombination having improved anti-oxidation and extreme pressureproperties.

Hydrocarbon oils are partially oxidized when contacted with oxygen atelevated temperatures for prolonged periods. The internal combustionengine is a model oxidator since it contacts a hydrocarbon motor oilwith air under agitation and at high temperatures. Moreover, many ofthe'metals (iron, copper, lead, nickel, etc.) manufactured into theengine and in contact with both the oil and air are excellent oxidationcatalysts which effectively increase the rate of oxidation. Theoxidation of motor oils is particularly acute in the modern internalcombustion engine which is designed to operate under heavy work loadsand at elevated temperatures.

The oxidation produces acidic bodies within the motor oil which arecorrosive to typical copper-lead and cadmium engine bearings. It hasalso been discovered that the oxidation of the oil additionallycontributes to piston ring sticking, the formation of sludges within themotor oil and an overall break-down of the viscosity characteristics ofthe lubricant.

Several effective oxidation inhibitors have been developed by thelubricant industries and their employment has been utilized in almostall of the conventional motor oils today. Typical of these inhibitorsare the sulfurized oil-soluble organic compounds, such as, sulfurizedsperm oil, sulfurized fatty esters, sulfurizedterpenes, sulfurizedpolybutenes and others. These inhibitors, while exhibiting excellentanti-oxidation and extreme pressure properties, are burdened by economicand oil contamination problems. It is preferred to maintain the sulfurcontent of the oil as low as possible while at the same time receivingthe benefits of anti-oxidation and extreme pressure properties. A needtherefore exists for an improved anti-oxidant that is stable at elevatedtemperatures, that can be employed at reduced concentrations,'that iseconomical and easy to produce and that has improved ecologicalproperties.

It is therefore an object of this invention to provide an improvedlubricating composition.

It is an additional object of this invention to provide a lubricantcomposition having improved antioxidation properties.

It is another object of this invention to provide a lubricantcomposition containing an anti-oxidant.

It is another object to provide a lubricant composition having improvedextreme pressure properties.

An additional object of this invention is to provide an improvedanti-oxidant for use in lubricating oils.

A further object of this invention is to provide a method of inhibitingoxidation of a motor oil.

Other additional objectswill become apparent from the followingdescription of the invention and accompanying claims.

SUMMARY OF THE INVENTION The aforegoing objects and their attendantadvantages can be realized by incorporating into a major portion of anoil of lubricating viscosity a combination of two compounds complementeach other in a synergistic manner resulting in a combination havingproperites superior to either additive alone.

With the instant combination, the amount of the sulfurized anti-oxidantnecessary'in order to impart the desired properties to a motor oil blendis significantly less than that amount needed when the bisphosphoramidecomponent is not present.

DETAILED DESCRIPTION OF THE INVENTION The compositions of this inventionare highly stable lubricants and exhibit excellent oxidation stability,perform well in extreme pressure tests such as the Timken load test anddisplay good anti-wear properties. These lubricants are quite useful inmotor oils for internal combustion engines, particularly in gasolineengines operated under elevated temperature conditions and for gear oilsand industrial lubricants.

The lubricant composition of this invention having improvedanti-oxidation, extreme pressure and antiwear properties comprises(1)from 85 to about 99 parts'by weight of a stable organic oil and oflubricating viscosity, (2) from 1 to 15 parts by weight of an organicsulfur compound containing from 3 to 40 weight percent sulfur as organicsulfides and/or polysulfides and (3) from 0.05 to 1 parts by weightof abisphosphoramide containing from 30 to 300 carbons. The ratio ofthe'organic sulfur-compound to the bisphosphoramide is maintainedbetween about 5 and 80:1.

The OrganicSulfur Compound The organic sulfur compounds which may beemployed in the practice of thisinvention include a wide range ofcompounds containing from 3 to 40 weight percent sulfur which ispresentwithin the compound as organic sulfides and polysulfides. The presenceof sulfur in other forms, such as, sulfonates, sulfates, etc. may existwithin the compound but is not included in thecalculation of the sulfurcontent of the organic sulfur compound. The'compound may containelements other than carbon, hydrogen and sulfur without adverselyaffecting properties of the composition and include elements such as,oxygen which may be present as ethers, ketones, carboxyls, esters,alcohols, etc., phosphorus, nitrogen present as amines, amides, imides,etc. as well as metals such as alkali metals, alkaline earthmetals,.etc.

One class of organic sulfur compounds which may be employed herein isthe sulfurized fatty esters. These compounds are prepared by contactingsulfur with an unsaturated fatty ester under elevated temperatures.Typical esters include C, to C alkyl esters of C -C unsaturated fattyacids, such as palmitoleic, oleic, ricinoleic, petroselinic, vaccenic,linoleic, linol'enic, oleos-' tearic, licanic, parinaric, tariric,gadoleic, arachidonic,

cetoleic, erucic, nervonic, etc. Particularly good results esters suchare obtained from animal fats and vegetable oils such as tall oil,linseed oil, olive oil, castor oil, peanut oil, rape oil, fish oil,sperm oil, etc.

Exemplary fatty esters include lauryl tallate, methyl oleate, ethyloleate, lauryl oleate, cetyl oleate, cetyl linoleate, laurylricinoleate, oleyl acetate, oleyl stearate, etc.

These compounds can be phosphosulfurized by contacting the fatty esterswith phosphorus pentasulfide along with the sulfur to produce asulfurizedphosphosulfurized ester. They may be further reacted with a Cto C alkylene polyamine having from 2 to nitrogens to impart varnishinhibiting properties to the lubricant.

Another class of organic sulfur compound which'may be employed in thepractice of this invention includes sulfurized terpenes, such assulfurized pine oil, sulfu rized terpinolene, sulfurized dipentene,sulfurized pinene, etc.

Sulfurized olefins such as C to C mono and poly ethylenicallyunsaturated aliphatic hydrocarbons may also be employed. Aromatic andalkyl sulfides may be employed such as dibenzyl sulfide, dixylyldisulfide, dicetyl sulfide, diparaffin wax sulfide and polysulfide, etc.Paraffin wax thiomers as described in U.S. Pat. No. 2,346,156 may beemployed.

Another type of organic sulfur compound which may be employed isamido-substituted dithiazole-thiones. These compounds are believed tohave the general structural formula:

f R NH-C:N

l s /o=s where R is a hydrocarbyl having from 8 to 24 carbons.Hydrocarbyl as defined herein is a monovalent organic radical composedessentially of hydrogen and carbon and may be aliphatic, aromatic, oralicyclic or combinations thereof and may be saturated or unsaturated.The preferred hydrocarbyl is an alkyl.

The amide substituted dithiazole compounds maybe prepared by reactingamino dithiazole-thione with a hydrocarbonyl chloride (RCOCL) in thepresence of an inert reaction solvent at moderate reaction conditions.

Another class of sulfurized compounds include C to C sulfurizedhydroxyesters. These compounds are prepared by reacting a fatty acid ofthe type mentioned supra with a C to C aliphatic epoxide and thencontacting the reaction product with sulfur under elevated conditions.

Another class of sulfurized compounds which may be advantageouslyemployed in, the practice of this invention comprise the polyalkylphenolsulfides. These compounds have the general structural formula:

(R)! l i )XJI (R):

wherein R is an alkyl having from 5 to 24 carbons, x is an integer from1 to 3;

y is an integer from 1 m5; and

z is an integer from 0 to 5. Compounds having the above formula areprepared by contacting an alkylated phenol with sulfur mono ordichloride in the proper portions under elevated temperatures. Thesecompounds can be thereafter reacted with phosphorus pentoxide, 'analkali or alkaline earth metal base or an amine.

A particularly useful sulfurized compound because of its multifunctionalproperties is a sulfurized metal phenate. These compound are prepared byreacting an alkyl phenol with sulfur and an alkaline earth metal base(e'.g., calcium hydroxide, barium hydroxide, calcium oxide, etc.) in thepresence of a mutual solvent. The resulting compounds have a generalizedstructural formula as follows:

CY 01 OY olQ I i, R 2i, R

wherein R is an alkyl group having from 8 to 35 carbons;-

y is an integer from 1 to 5;

z is an integer from 0 to 15;

Y is the same or different constituent selected from H or /2 M where theratio of H to k M is proportional to the ratio of M to alkyl phenolreacted; and

M is an alkaline earth metal.

The above formula represents a broad and simplified version of thesulfurized compounds and it should be recognized that minor amounts ofcompounds not defined by the above equation may be present in thereaction p'roduct mixture. The mutual solvent employed in the abovereaction can comprise any stable organic liquid having appreciablesolubility for both the alkaline earth metal base and alkylphenol.Exemplary solvents include ethylene glycol, 1,4-butanediol, etc.

Sulfurized alkaline earth metal phenates prepared by reacting analkylated phenol with an alkaline earth metal base to form anintermediate metal phenate which is then sulfurized may be successfullyemployed.

These compounds are more specifically described in U.S. Pat. No.2,360,302.

The Bisphosphoramide wherein X is the same or different element selectedfrom nitrogen or oxygen;

Y is the same or different element selected from oxygen, sulfur ornitrogen when X is nitrogen or nitrogen when both Xs are oxygen;

n is an integer equal to 1 when' Y is oxygen or sulfur and 2 when Y isnitrogen;

m is an integer equal to 11-1, i.e., 0 when X is oxygen and 1 when X isnitrogen;

R is a hydrocarbylene or dihydrocarbylene having from 2 to 18 carbonsand preferably from 2 to 8 carbons or the halo, keto, t-amino, amido,mononitro, or alkoxy derivative thereof;

R is the same or different constituent selected from hydrogen when Y isnitrogen or a hydrocarbyl having from 1 to 24 carbons and preferablyfrom 6 to 20 carbons or the halo, keto, t-amino, amido, mono-nitro oralkoxy derivative thereof; and

R is the same or different hydrocarbyl having 1 to 24 carbons or ahydrocarbylene having from 2 to 18 carbons and preferably from 2 to 8carbons with one end of each R bonding to the other R or to said R whenR is a dihydrocarbylene or the halo, keto, t-amino, amido, mono-nitro oralkoxy derivative of either of the above.

As referred to herein, hydrocarbyl is a monovalent organic radicalcomposed essentially of hydrogen and carbon and may be aliphatic,aromatic, or alicyclic or combinations thereof; e.g., aralkyl, alkyl,aryl, cycloalkyl, alkylcycloalkyl, etc., and may be saturated orethylenically unsaturated (one or more double bonded carbons, conjugatedor nonconjugated). The preferred hydrocarbyl is an alkyl. Thehydrocarbylene, as defined herein, is a divalent hydrocarbon radicalwhich may be aliphatic, alicyclic, aromatic or combinations thereof;e.g., alkylene, arylene, alkylarylene, aralkylene, alkylcycloalkylene,cycloalkylarylene, etc., having its two free valences on differentcarbon atoms. The preferred hydrocarbylene is an alkylene. Thedihydrocarbylene, as defined herein is a quadruple valent hydrocarbonradical which may be aliphatic, alicyclic, aromatic or combinationsthereof; e.g., dialkylene, diarylene, dialkylarylene, diaralkylene,dicycloalkylene, etc., having less than three of its free valences on asingle carbon atom and preferably having its four free valences ondifferent carbon atoms.

The various derivatives of the R, R and R groups as referred toherein'mean the substitution of the functional group (halo, keto, etc.)on or within the R, R or R chain with less than percent and preferablyless than 5 percent of the available sites substituted.

The above structural formula represents a simplified version of thereaction product. The reaction product is not a pure compound havingonly one single structure, but, rather, is a mixture of numerousamidophosphorous compounds. The above formula indicates that there aretwo phosphorus atoms in each molecule.

However, because the composition is a mixture of compounds, it isrecognized that some molecules may have more than two phosphorus atomssuch as polyphosphoramides and at the same time some molecules may haveonly one phosphorus atom as in monophosphoramide. Thus, it is apparentthat while the above chemiyldicyclohexylphosphorothioamide);trimethylene dipiperazine bis (tetracocophosphoramide); diethyleneglycol bis(tetracocophosphoramide); N,N-diethyl-l ,3- propane diaminebis (tetracocophosphoramide); piperazine bis(dilaurylphosphorthioamide); etc.

The bisphosphoramides are prepared by reacting phosphorus oxychloridewith a difunctional secondary amine or glycol and a monofunctionalamine, alcohol or mercaptan. The reaction can be conductednoncatalytically by merely contacting the three reactants within asuitable reaction vessel at a temperature from 0 to 200C andpreferablyfrom 20 to C. The reaction pressure is not critical exceptthat it is preferred to apply sufficient pressure on the system tomaintain liquid phase conditions. Generally, the pressure will rangefrom 10 to 50 0 psia and preferably from 14 to 35 psia. l

The difunctional amine or alcohol forms the bridging group between thetwo phosphorus atoms as shown in the structural formular supra. Themonfunctional amine, alcohol or mercaptan, on the other hand, reactswith remaining halogens on the phosphorus oxychloride molecules to formthe four terminal groups extending from the phosphorus atoms.

The difunctional compounds which may be employed in the practice of thisinvention have the following general structure:

The definition of X, R, R and m ispresented supra under the descriptionof the bisphosphoramide general formula. The dotted lines aboveillustrate the possible heterocyclic bonding of the R and R groups whenX is nitrogen. For example, when R is a .dihydrocarbylene or substituteddihydrocarbylene, the two R groups bond to the center R group along path(1). Exemplary compounds of this structure include methylenedipiperazine, dimethylene dipiperazine, trimethylene dipiperazine,tetramethylene dipiperazine, diethyleneoxydipiperazine,bis(diethyleneoxy) dipiperazine, etc. When R is a hydrocarbylene, one Rgroup along path (2) forms a heterocyclic ring encompassing the two Xatoms. Exemplary compounds of this structure include piperazine,2,5dichloropiperazine, 2,5 dimethylpiperazine,

etc.

Secondary diamines other than heterocyclic diamines may also be employedin the practice of this invention. In this embodiment, the R groups arehydrocarbyl or substituted hydrocarbyl radicals and R is ahydrocarbylene or substituted hydrocarbylene. Exemplary compounds ofthis type include N,N'diphenylethylenediamine, N,N'-diethyl-o-tolidine;N,N'-diethylo-dianisidine, N,N-diethyl-l,3-propanediamine, N,N'-di(p-chlorophenyl)ethylenediamine, N,N'-diethylcyclohexylenediamine,etc.

Difunctional compounds having two hydroxy groups (X in the above formulais oxygen) include C to C primary diols such as trimethylene glycol,ethylene glycol, diethylene glycol, triethylene glycol, propyleneglycol, dipropylene glycol, tetramethylene glycol, npropane-1,3-diol,2-butene-1,4-diol, 2,2'thiodiethanol, neopentyl glycol, hydroquinone,chlorohydroquinone, naphthohydroquinone, phenyl-l,2-ethanediol, 2-

anilino-l ,4-naphthohydroquinone, 2,7-dihydroxynaphthalene, etc. Thepreferred difunctional hydroxy reactants have from 2 to 12 carbons.

Difunctional compounds having one hydroxy group and one secondary aminegroupmay also be employed. In this embodiment one of the Xs in the aboveformula is oxygen and the other X is nitrogen. Exemplary com- The monofunctional compounds which may be employed in the practice of thisinvention have the following general formulai 0,! Y e H wherein R n andY are defined supra under the description of the'bisphosphoramidegeneral formula. Exemplary monofunctional compounds include C to Cmonohydroxy alcohols, monomercaptans and primary or secondarymonoamines. Exemplary monohydroxy alcohols include, methanol, propanol,butanol, pentanol, hexanol, octanol, cyclohexanol, 2-methylcyclohexanol, phenol, cresol, naphthol, p-chlorophenol, pmethylphenol,etc. Exemplary mercaptans include methyl mercaptan, propyl mercaptan,butyl mercaptan, hexyl mercaptan, cyclohexyl mercaptan, naphthylmercaptan, p-butylphenyl mercaptan, B naphthyl mercaptan, etc. Exemplarymonoamines include primary alkyl-, amines such as heptylamine,octylamine, dodecylamine, tetradecylamine, hexadecylamine,octadecylamine, etc; secondary alkylamines such as, diheptylamine,N-ethyl-N-hexylamine, N-hexyl-N-octylamine, N,N-dioctylamine, andN-butyl-N-hexylamine, etc.; primary and secondary cycloalkyl andalkylcycloalkylamines such as 2-ethylcyclohexylamine, N-ethyl-N-cyclohexylamine, N-methyl-N-cyclohexylamine, N-propyl-N-cyclohexylamine,N,N-dicyclohexylamine, N-ethyl-N-cyclopentylamine,2-propyl-3-ethylcyclohexylamine, etc.,; and primary and secondary aryland alkylarylamines such as methylaniline, toluidine,N-ethyl-N-phenylamine, p-anisidine, nitroaniline, diphenylamines,N/,N-propylphenylamine, 2,4,6 trichloroaniline, N-octyl-N-phenylamine,p-phenetidine, etc.

Particularly preferred monohydroxy alcohols, mono mercaptans andmonamines are prepared from animal and vegetable oils and fats. Typicalnatural oils and fats which may be employed in preparing themonofunctional compounds include coconut oil, corn oil, rape oil, castoroil, peanut oil, cottonseed oil, linseed oil, olive oil, palm oil,safflower oil, soybean oil, tall oil, sperm oil, tallow, lard, etc.These oils are generally comprised of a mixture of saturated andunsaturated fatty acids such as caprylic, capric, lauric, myristic,pal-' mitic, stearic,'arachidic, palmitoleic, oleic, ricinoleic,linoleic, eleostearic, etc. The fatty acids are converted into thecorresponding primary or secondary amine, alcohol or mercaptan byconventional processing means.

The preferred monofunctional compounds are the C -C primary andsecondary vegetable oil amines such as caprylamine, dicaprylamine,laurylamine, dilaurylamine, myristylamine, dimyristylamine,palmitylamine, dipalmitylamine, etc. and mixtures thereof.

The preferred bisphosphoramides of this invention are prepared byreacting a primary or secondary'monoamine having from 2 to 40 carbonswith piperazine and phosphorus oxychloride. The compounds have thefollowing general structure:

wherein R is hydrogen or preferably a hydrocarbyl having from 2 to 20carbons; and

R is a hydrocarbyl having from 2 to 20 carbons.

The bisphosphoramides may be prepared by either a batch or continuousprocessing scheme. In a typical batch process, a reaction vessel,preferably constructed or lined with a corrosive resistant material suchas glass, teflon, etc., is charged with a suitable inert reactionsolvent and the difunctional and monofunctional compounds. The contentsof the reactor are stirred to disperse the reactants within the reactionsolvent. The

phosphorus oxychloride is then introduced into the reaction vessel incontact with the other reactants. The reaction takes place spontaneouslyupon the contacting of these reactants to produce the bisphosphoramide.Since the reaction is also exothermic, care must be taken in theintroduction of the reactants in order to avoid rapid increases inlocalized temperatures. Preferably, the phosphorus reactant isintroduced into the vessel at a rate of 5 to 25 mols per 50 mols ofdifunctional and monofunctional compounds per hour. This addition rateis not critical to the practice of this invention and only provides aconvenient method of introducing the phosphorus reactant into the systemwithout the problems of spontaneous boiling. For example, the phosphorusoxychloride may be charged to the reaction vessel before either thedifunctional or monofunctional reactant, or in another alternativeembodiment, the reactants may be charged to the vessel in anintermittent manner. The reaction can also be conducted adiabaticallywith the heat of reaction effecting the necessary temperature increasein the system.

In preferred embodiments, when a mercaptan or alcohol monofunctionalreactant is employed, these compounds are contacted with the phosphorusoxychloride prior to the introduction of the difunctional amine or atleast before the stoichiometric amounts of difunctional amine isintroduced into the reaction medium. In this manner, the less reactivemercaptan or alcohol is allowed to partially react with the phosphorusoxychloride prior to the introduction of the more reactive difunctionalamine. When a dihydroxy difunctional reactant and amine monofunctionalreactants are employed, it is, likewise, preferred to introduce the lessreactive dihydroxy reactant into contact with the phosphorus oxychlorideprior to the addition of the amine reactant.

During the course of the reaction, hydrogen chloride is released as aby-product. This by-product can be stripped from the reaction mediumduring or after the completion of the reaction. While stripping may be aconvenient method for removing the material, the conditions employedduring the stripping steps in many instances have an adverse effect onthe product bisphosphoramide. Therefore, it is preferred to complex orneutralize the hydrogen chloide within the reaction medium concomitantwith its formation. I have found that the complexing or neutralizationstep can be accomplished by admixing a stable basic compound or acidacceptor within the reaction medium. Exemplary acid acceptors include Cto C trialkyl amines such as trimethylamine, triethylamine,tripropylamine, triisopropylamine, tributylamine, etc., basic hetarenes,such as pyridine, quinoline, picoline, pyrazine, etc., as well as basicmetal compounds such as magnesium oxide, calcium oxide, calciumcarbonate, magnesium carbonate, alkaline earth metal hydroxides such asmagnesium hydroxide, calcium hydroxide, barium hydroxide, etc., andalkali hydroxides such as sodium hydroxide, potassium hydroxide andlithium hydroxide or alkali carbonate or bicarbonate.

The preferred acid acceptors are the trialkylamines and hetarenes sincewater is not produced in the neutralization of the hydrogen chlorideby-product. The presence of water is the system is to be avoided sinceit may react with the phosphorus oxychloride reactant.

The crude bisphosphoramide can then be filtered to remove the liquidreaction medium and unreacted reactants. Although filtering ispreferred, it is recognized that alternative purification steps can beperformed such as extraction, stripping, etc.

As discussed supra, the 'reaction is preferably conducted in thepresence of an inert stable reaction solvent. Exemplary reactionsolvents which may be employed in the practice of this invention includeC to C aliphatic or aromatic hydrocarbons such as hexane, octane,nonane, benzene, toluene, naphthalene, ethylcyclohexane, etc.,halogenated hydrocarbons, hydrocarbon esters, hydrocarbon ethers, etc.,may be employed.

The concentration of the various reactants within the reaction mediumcan vary over a wide range depending upon the reactants chosen, thereaction conditions, vessel construction, processing scheme, etc.Generally, however, the reactants will be present in the amounts shownin the following Table 1.

(1) Based on the amount introduced into the reaction medium.

The molar ratio of the reactants introduced into the reaction mediumwill generally vary from 3 to 5 mols of monofunctional compound and 0.4to 0.6 mols of difunctional compound per mo] of phosphorus compound.Preferably the reactants are present in substantially stoichiometricamounts.

The lubricant composition is prepared by simply admixing throughconventional dispersing techniques, the

appropriate amount of organic sulfur compound and bisphosphoramidewithin a suitable lubricating oil. The selection of the particular baseoil, organic sulfur compound and bisphosphoramide, as well as theamounts and ratios each, depends upon the contemplated appli cation ofthe lubricant and the presence of other additives. Generally, however,the amount of organic sulfur compound in the lubricating oil will varyfrom 0.5 to 10 and usually from 1 to 6 weight percent in mostapplications and the bisphosphoramide will range from 0.05 to 5 andusually from 0.1 to 1 weight percent based on the weight of the finalcomposition. The ratio of organic sulfur compound to bisphosphoramidewill generally vary from 2 to 30:1 and usually from 5 to 20:1.

The lubricating oil which may be employed in the practice of thisinvention includes a wide variety of hydrocarbon oils. Other oilsinclude lubricating oils derived from coal products and synthetic oils,e.g., alkylene polymers (such as, polypropylene, butylene, etc. andmixtures thereof) alkylene oxide-type polymers (e.g. alkylene oxidepolymers prepared by polymerizing alkylene oxide such as ethylene oxide,propylene oxide etc., in the presence of water or alcohol, e.g. ethylalcohol), carboxylic acid esters (e.g. those which wereprepared byesterifying carboxylic acids such as adipic acid, azelaic acid, subericacid, sebacic acid, alkenylsuccinic acid, fumaric acid, maleic acid,etc., with the alcohol such as butyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, pentaerythritol, etc., liquid esters of phosphorus,such as trialkyl phosphate (tributyl phosphate), dialkylaryl phosphate,triaryl phosphate (tricresyl phosphate) etc. alkylbenzenes, polyphenyls(e.g., biphenyls and terphenyls), alkylbiphenyl/ethers, esters andpolymers of silicon, e.g., tetraethyl. silicate, tetraisopropylsilicate, hexyl(4-methyl-2-pentoxy) disilica'te, poly(methyl)siloxaneand poly(methylphenyl) siloxane, etc. The lubricating oils may be usedindividually or in combinations whenever miscible or whenever made so byuse of mutual solvents. Thelubricating oils generally have a viscositywhich ranges from 50 to 5000 SUS (Saybolt Universal Seconds) and usuallyfrom to 1500. SUS at 100F.

In addition to the sulfurized organic compound and the bisphosphoramide,other additives may be successfully employed within the lubricatingcomposition of this invention without affecting its high stability andperformance over a wide temperature scale. One type of additive whichmay be employed is a rust inhibitor. The rust inhibitor is employed inall types of lubricants to suppress the formation of rust on the surfaceof metallic parts. Exemplary rust inhibitors include, sodium nitrite,alkenylsuccinic acids and derivatives thereof, alkylthio-acetic acid andderivatives thereof, substituted imidazoles, amine phosphates, etc.

Other types of lubricating oil additives which may be employed in thepractice of this invention include antifoam agents (e.g., silicones,organic copolymers), stabilizers, anti-stain agents, tackiness agents,anti-chatter agents, dropping point improvers, anti-Squawk agents,lubricant color correctors, extreme pressure agents, odor controlagents, dispersants, detergents, anti-wear agents, such as tricrescylphosphate and zinc dithiophosphate esters, etc.

In many instances it may be advantageous to form concentrates of theorganic sulfur compound and the bisphosphoramide with or without acarrier liquid. The employment of concentrates provides a .convenientmethod of handling and transporting the compounds for their subsequentdilution and use. The concentration of the two components within theconcentrates may vary from 50 to 98 weight percent of sulfurized organiccompound, 1 to weight percent bisphosphoramide and O to 45 percentdiluent oil, although it is preferred to maintain the concentrationbetween about 75 and 95 weight percent organic sulfur compound, 4 to 15weight percent bisphosphoramide and O to 21 weight percentdiluent oil.

LUBRICANT PERFORMANCE The presence of the bisphosphoramide within thelubricant composition promotes the extreme pressure and anti-oxidationproperties of the sulfurized organic compound. With this combination,less of the sulfurized compound is necessary in the lubricant to realizethe desired anti-oxidant and extreme pressure properties.

In addition to promoting the anti-oxidation and extreme pressureproperties of the organic sulfur com-,

pounds, the bisphosphoramides impart substantial antiwear properties tothe lubricant and in many instance surpass the anti-wear propertiesimparted by tricresyl phosphate and zine dihydrocarbyldithiophosphate.

It should be well recognized that the organic sulfur compound andbisphosphoramide mixture may be successfully employed in lubricantapplications wherein oxidation, extreme pressures or metal wear is aproblem. Thus, the mixture may be employed in lubricating oil such asmotor oils, turbine oils, gear oils, railroad diesel engine oils,tractor and truck diesel engine oils, two cycle gasoline engine oil,cutting oils, drilling oils, lapping, grinding and honing oils,lubricating oils for pneumatic devices such as jackhammers, sinkers,stoppers, drifters and down hole drills.

The organic sulfur compound and bisphosphoramide mixture may also beuseful in mist lubricants. In a mist lubricating system the lubricant isatomized in a mist generator and carried through conduits by an airstream. The lubricant droplets are coalesced and collected at thelubricant site. Such systems permit simultaneous lubrication of severalremote lubrication points from a central lubricant reservoir.

The following examples are presented to illustrate the practice ofspecific embodiments of this invention and should not be interpreted aslimitations upon the scope of this invention.

EXAMPLE 1 I This example is presented to illustrate the preparation of arepresentative bisphosphoramide of this invention. A two-liter resinflask equipped with a dropping funnel, gas tube, stirrer and thermometeris charged with 315 g. of toluene, 303 g. of triethylamine, 754 g. ofdicocoamine and 43 g. of piperazine. The contents of the flask arestirred and heated to a temperature of 50C to uniformly disperse thedicocoamine and piperazine within the toluene solution. The contents arecooled to 29C and 155 g. of phosphorus oxychloride are slowly added tothe mixture through the dropping funnel for a period of approximately 1hour.

A stream of nitrogen gas is passed through the reaction medium at a rateof about 200 milliliters per minute.

After the phosphorus oxychloride has been charged to the reactor, thecontents are heated to reflux at a temperature of approximately l20F fora period of about 1.5 hours. At the end of the reaction period thereactor contents are cooled and filtered to recover the filtrate. Thefiltrate is then washed with 700 ml. of water until the filtrate is freeof chloride. The filtrate is stripped of toluene and the remaining waxyresidue is calculated to have the following structural formula:

where Coco is a mixture of alkyl groups derived from coconut oil fattyacids.

An analysis of the product reveals the following:

This example is presented to demonstrate the preparation of piperazinebis (N,N'-diethyl-N,N'-dicyclohexylphosphoramide). In the preparation, a2-liter resin flask equipped with a dropping funnel, gas tube, stirrerand a thermometer is charged with 380 g. of toluene, 606 g. oftriethylamine, 510 g. of ethylcyclohexylamine and 84 g. of piperazine.The mixture is heated to a temperature of C and stirred to disperse theamine reactants within the toluene. Phosphorus oxychloride is thenslowly introduced into the reaction medium at a rate of 300 g. per hour.During the addition of the phosphorus oxychloride the mixture ismaintained in dry state by passing 200 ml. per minute of nitrogen gasthrough the reaction medium. After 310 g. of phosphorus oxychloride havebeen introduced into the vessel, further addition is terminated and thereactor contents are heated to a temperature of approximately 120'Cunder refluxing conditions. The mixture is refluxed for a period of 2hours. The flask is then cooled and the contents filtered. The filtrateis washed with water to remove the chloride and thereafter stripped oftoluene. The bisphosphoramide product is calculated to have thefollowing structure:

In this example, diethylene glycol bis(tetracocophosphoramide) isprepared. A 1 liter resin flask equipped with a stirrer, turned downcondenser, thermometer, dropping funnel and a nitrogen gas inlet tube ischarged with 64 grams of triethylamine, 10.6 grams of diethylene glycol,600 milliliters of toluene and 151 grams of phosphorus oxychlmidedi(hydrogenated coco) amine (mol wt. 377). The mixture is heated toabout 50C and stirred to dissolve its reactants within the toluene.Phosphorus oxychloride is then slowly introduced into the vessel,further addition is terminated and the flask is heated to a temperatureof 100-110C under refluxing conditions for a period of about 7 /2 hours.The flask is washed with water to remove the chloride ions andthereafter stripped of toluene. The bisphosphoramide product iscalculated to have the following structure.

wherein Coco is the coconut oil fatty radical.

An analysis of the bisphosphoramide reveals the following:

Calculated Found (weight (weight Nitrogen 3.3 3.16 Phosphorus 3.6 3.8

EXAMPLE 4 An analysis of the bisphosphoramide reveals the following:

Calculated Found (weight (weight Nitrogen 4.9 3.5 Phosphorus 3.6 3.7

EXAMPLE 5 The procedure of Example 1 is repeated except thattrimethylene dipiperidine is substituted for the piperazine and thefollowing amounts employed.

Moles Grams Trimethylene 4,4' dipiperidine 42 0.2 Triethylamine 111 1.1Toluene 500 -Continued Grams Moles Dicocoamine 302 0.8 62 0.4

The resulting bisphosphoramide is calculated to have the followingstructure:

An analysis of the compound reveals the following:

Calculated Found 9 (weight 7:) (weight i Nitrogen 4.6 I 4.0 Phosphorus3.4 4.8

EXAMPLE 6 EXAMPLE 7 The preparation of a sulfurized calcium phenatewhich may be employed in the practice of this invention is illustratedby this example. A 3 liter reaction vessel equipped with a stirrer,thermometer, condenser and dropping funnel is charged with 661 grams ofneutral oil, 747 grams of tetrapropylene phenol, 197 grams of sulfur and144 grams of calcium hydroxide. The mixture is heated to 260F under avacuum of 10 mm Hg and vigorously agitated. Thereafter 0.346 grams ofethylene glycol are added to the mixture over a 20 minute period and thetemperature allowed to increase to about 300F. The temperature ismaintained at 300F under a 10 inch Hg vacuum for a period of 2 hours.Thereafter, the temperature is increased to 386F over a 2% hours periodwhile simultaneously reducing the pressure to 11 mm Hg. The contents aremaintained at a temperature of 386F and a pressure of 1 1 mm Hg for 15minutes and thereafter cooled and filtered.

A sample of the crude sulfurized metal phenate is filtered throughdiatomaceous earth and found to contain 5.54 wt. percent sulfurand 4.4wt. percent calcium. The product had an alkalinity value of 1 14.3 mgKOH/gm.

EXAMPLE 8 This example is presented to illustrate the'effectiveness ofthe combination of a sulfurized organic compound and a bisphosphoramidein suppressing oxidation over the use of either component individually.The oxidation test as employed herein measures the resistence of thetest sample to oxidation from pure oxygen with a Dornte-type oxygenabsorption apparatus (R.W. Dornte, Oxidation of White Oils, Industrialand Engineering Chemistry, Vol. 28, p. 26, 2936). The conditions areatmosphere of pure oxygen exposed to the test oil maintained at atemperature of 340F. The time required for 100 grams of the test sampleto remove 1000 ml. of oxygen is observed and reported in the follwoingTable 2.

In order to simulate the oxidation occurring in an internal combustionengine, a mixture of various soluble metal-naphthenates, typifying themetal analysis frequently encountered in crankcase oils, is mixed withthe test oil.

The experimental samples subjected to the above oxidation test consistof the following: Sample A contains 98 weight percent of a neutral oilhaving a viscosity of 480 SUS at 100F., 1.8 weight percent ofa-sulfurized alkyl tallate ester containing about 10 percent sulfur and0.2 weight percent of a bisphosphoramide .prepared by the method ofExample 1. This sample is designated as containing the combination ofadditives. Sample B contains 98 weight percent of an identical neutraloil as used in Sample A, 1.9 weight percent of an identical sulfurizedtallate as used in Sample A and 0.1 weight percent of tricresylphosphate. The sample is designated as containing the sulfurizedcompound only. Sample C contains 99.8 weight percent of the identialbase oil as used in Sample A and 0.2 weight percent of an identicalbisphosphoramide as used in Sample A. This sample is designated ascontaining the bisphosphoramide only. Sample D is 100 percent of thebase oil employed in the above samples and is designated as containingno additive". The results of the oxidation test with the above sampleare reported in the following Table 2.

TABLE 2 OXIDATION TEST Sample Additive Package Oxidation Life (hr.)

A Combination 5.7 B Sulfurized Compound only 3.3 C Bisphosphoramide only0.5 D No additive 0.5

EXAMPLE 9 The effectiveness of the instant combination in improving theextreme pressure properties of a lubricant over any of the componentsindividually is illustrated in this example. In this test a sample ofthe composition is subjected to a Timken Test (ASTM 2782-69T) todetermine the load carrying capacity of the lubricant. This test measurethe maximum load or pressure which containing a combination ofadditives. Sample B is identical to Sample A except that nobisphosphoramide is present. This sample is designated as containing thesulfurized compound only. Sample C isv the same as Sample A except thatno sulfurized compound is present. This sample is designated ascontaining the bisphosphoramide only. The results of the Timken testwith the above samples is repeated in the following Table 3.

TABLE 3 TIMKEN TEST Sample Additive Package Load Passing (lb) ACombination B Sulfurized Compound only 45 C Bisphosphoramide only 10 Theabove table illustrates the effectivenessof teh combination ofsulfurized compound and bisphosphoramide in effecting superior passingloads over either component individually. The Timken load is indicativeof the extreme pressure properties of the lubricant with a higher loadconnoting superior E.P.

EXAMPLE 10 This example is presented to illustrate the effectiveness ofthe bisphosphoramides in promoting the extreme pressure properties ofrailroad oils containing sulfurized alkaline earth metal phenates. Inthis example several samples are subjected to a silver thrust washertest. The apparatus of this test is prepared by soldering to a back ofsoft steel washer, a silver test washer composed of 99.9percent puresilver. Both the silver and the steel backing are nominally /8 inch inthickness, 1.3 inches OD. and 1.0 inch ID. The silver surface is groovedby three equally spaced 5 inch slots. A 0.0l-inch-deep and 1/32inch-wide slit is cut across the center of each of the three raisedsilver surfaces.

The silver washer is annealed after machining and after each use toremove any work hardening in the silver. The annealing is carried out at650F for one half hour and allowed to cool to room temperature.Following annealing, both sides are surface lapped to obtain a smoothflat surface of approximately 9-12 micro inches finish.

The steel test specimen is made to duplicate the metallurgy of the wristpin steel in the EMD locomotive engine. The material is AISI Steel No.862011. Heat treatment to a minimum hardness of 58 Rockwell C isachieved by carburizing for 0.04-0.05 finish case depth, pit cool;reheating to 1,475F. and oil quenching; followed by tempering at 400F.for 8 hours. Both sides are finished-lapped to a finish of 3-5microinches. Nominal dimensions are 1% inches OD, 0.9 inch ID, and 0.2inch thick.

A motor-driven mechanism is used to obtain oscillatory motion at thetest surfaces. A 20 cc. sample of test oil is employed in the oil cup,the apparatus assembled and the oscillatory motion begun. The apparatusis run for'lO minutes without heating. At the end of the minutes, thereis a 35 minute heatup as the temperature is raised to 350F., followed by45 minutes of constant temperature operation at 350F. The load duringthe test is maintained contiuously at 4280 psi at the bearing surfacesby means of a calibrated spring.

The power, as measured in watts, required to maintain the oscillatorymotion at the test surface is measured and reported in the followingTable 4. The power requirement of the motor is indicative of extremepressure properties of the lubricant with a lower power requirementconnoting a superior E.P. lubricant.

Four test lubricants are subjected to the above silver thrust washertest. Test sample A comprises (1) 99 weight percent of a 40 gradelubricating oil having a viscosity index of 73 and containing aconventional succinimide dispersant and 79 millimole per kilogram of oilofa carbonated sulfurized calcium polypropylene phenate containing 9.25weight percent calcium, 3.73 weight percent sulfur and 4.6 weightpercent equivalent CO and (2 1 weight percent of a cross-sulfurizedalkyltallate and cracked wax olefin. This sample is referred to ascontaining a sulfurized calcium phenate and a sulfurized ester only.Test sample B comprises (1 98.8 weight percent of the lubricating oilcontaining a succinimide dispersant employed in test oil A, and 79millimoles per kilogram of the sulfurized calcium phenate as employed intest oil A, (2 1 weight percent of the sulfurized ester as employed intest oil A, and (4) 0.2 weight percent of a bisphosphoramide of the typeprepared by the method of example 1. Test oil C comprises 100percent ofthe test oil as employed in sample A and 34 millimoles per kilogram ofoil of a sulfurized calcium polypropylene phenate containing about 4.5wt. percent calcium and 4.9 wt. percent sulfur. This test oil isreferred to herein as containing a sulfurized calcium phenate only. Testsample D comprises 99.8

weight percent of test oil C plus 0.2 weight percent of abisphosphoramide prepared by the method of example 1. This test sampleis referred to as containing a sulfurized calciumphenate and abisphosphoramide.

The above test samples are subjected to the silver thrust washer test asdefined above with the results being reported in the following Table 4.

TABLE 4 SILVER THRUST WASHER TEST Sample Additives Power (watts) ASulfurized calcium phenate Sulfurized ester 250 B Sulfurized calciumphenate sulfurized ester Bisphosphoramide 185 C Sulfurized calciumphenate 230 D sulfurized calcium phenate Bisphosphoramide 177 I claim:

1. A concentrate comprising (a) from 50 to 98 weight percent of anoleophilic organic sulfur compound or mixture thereof containing from 3to 40 weight percent-sulfur and selected from the group consisting ofsulfurized esters, sulfurized terpenes, sulfurized olefms, aromaticsulfides, alkyl sulfides, amidosubstituted dithiazole-thiones,sulfurized hydroxy esters, polyalkylphenol sulfides and sulfurizedalkaline earth metal phenates, (b) from 1 to 20 weight percent of abisphosphoramide prepared by contacting within a liquid phase reactionmedium (1 phosphorus oxychloride (2 a difunctional compound having thestructure:

nx n xrr om-4R2)...

wherein X is the same of different element selected from nitrogen oroxygen, R is a hydrocarbylene having from 2 to 18 carbons or adihydrocarbylene having from 2 to 18 carbons; m is an integer equal to 1when X is nitrogen and 0 when X is oxygen; R is (a) the same ordifferent hydrocarbyl having from 1 to 24 carbons or (b) ahydrocarbylene having from 1 to 18 carbons with one end of each Rhydrocarbylene bonding to the other R hydrocarbylene or to said R when Ris a dihydrocarbylene; and (3 a monofunctional compound having theformula:

wherein Y is the same of different element selected from (i) oxygen,sulfur or nitrogen when X is nitrogen or (ii) nitrogen when both Xs areoxygen; n is an integer equal to 1 when Y is oxygen or sulfur and 2 whenY is nitrogen; and R, is the same or different constitutent selectedfrom (i) hydrogen when Y is nitrogen or (ii) a hydrocarbyl; saidcontacting being conducted at a temperature of about 20 to C and atapressure sufficient to maintain a liquid reaction medium, and (c) from0 to 45 weight percent of a diluent oil.

2. The composition defined in claim 1 wherein said difunctional compoundis selected from piperazine, methylene-dipiperazine,dimethylenepiperazine and trimethylenedipiperazine.

3. The composition defined in claim 1 wherein said oleophilic organicsulfur compound is selected from the group consisting of sulfurized C toC alkyl esters of C to C fatty acids, sulfurized C to C unsaturatedaliphatic hydrocarbons, C to C sulfurized hydroxyesters, polyalkylphenolsulfides, and sulfurized metal phenates.

4. The composition defined in claim 3 wherein said bisphosphoramide isthe reaction product of dicocomaine with piperazine and phosphorusoxychloride.

5. A lubricating composition comprising (1 a major amount of an oil oflubricating viscosity, (2 from 0.5 to 10 weight percent of an oleophilicorganic sulfur compound or mixture thereof containing from 3 to 40weight percent sulfur and selected from the group consisting ofsulfurized esters, sulfurized terpenes, sulfurized olefms, aromaticsulfides, alkyl sulfides,- amidosubstituted dithiazole-thiones,sulfurized hydroxy esters, polyalkylphenol sulfides and sulfurizedalkaline earth metal phenates, and (3 from about 0.05 to 5 weightpercent of a bisphosphoramide prepared by reacting (a) phosphorusoxychloride (b) a difunctional compound 'of the formula:

ma n-x11 (Rimom wherein X is the same or different element selected fromnitrogen or oxygen;

R is a hydrocarbylene having from 2 to 18 carbons or a dihydrocarbylenehaving from 2 to 18 carbons; m is an integer equal to 1 when X isnitrogen and when X is oxygen; R is the same or different hydrocarbylhaving from 1 to 24 carbons or a hydrocarbylene having from I to 18carbons with one end of each R hydrocarbylene bonding to the other Rhydrocarbylene or to-said R when R is a dihydrocarbylene; and (c) amonofunctional compound having the formula:

oxygen, sulfur or nitrogen when X is nitrogen or 8. The compositiondefined in claim 5 wherein said oil of lubricating viscosity is presentin major amounts, said organic sulfur compound is present at aconcentration of l to 6 weight percent and said bisphosphoramide ispresent at a concentration of 0.1 to 1 weight percent.

9. The composition defined in claim 5 wherein said organic sulfurcompound is a sulfurized C, to C alkyl ester of an unsaturated C to Cfatty acid.

10. The composition defined in claim 9 wherein said oil has a viscosityof 50 to 5000 SUS at a temperature of F.

11. A composition of matter comprising a major portion of an oil oflubricating viscosity containing 1. from 0.5 to 10 weight percent of anoleophilic organic sulfur compound containing from 3 to 40 weightpercent of sulfur present as organic sulfides or polysulfides ormixtures thereof and selected from a C to C alkyl ester of a C to Cunsaturated fatty acid or a sulfurized alkaline earth metal phenate; andI 2. from 0.05 to 5 weight percent of a bisphosphoramide having theformula:

(NRsRDa wherein R is hydrogen or a hydrocarbyl having from 2 to 20carbons; and

R is a hydrocarbyl having from 2 to 20 carbons.

@33 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.38592l9 Dated January 7, 9 5

I BRUCE W. HOTTEN It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Title page, Col. 1, line 6, 7 and 8, should read --Notice:

The portion of the term of this patent subsequent to March 5, 1991 hasbeen disclaimed.--

Col. 2, line 1. 1, "properites" should read --prop erties--.

Co 5, line 13, "having from 2 to 18" should read having from 1 to l8--;

Col. 5, line 15, "to the other R should read -to the other 13 Col. 6,line 20, "monfunctional" should read --monofunctional--.

' Col. 7, line 8, "Bhydroxyethy1e" should read ---B-hydroxyethyl-- Col.9, line 19, "is the system" should read --i n the system-- Col. 15, line7, 26, 2936" should read --p. 26, 1936- Col. 16, line 28, "teh" shouldread --the- Col. 17, line 7, "contiuously" should read --continuously-.Col 1.7, line 6 1, "repersent" should read --represent-- Col. 18, line18, "of different" should read ordifferent-- Col'. 18, line 31 "ofdifferent" should read --or different- Col. 19, lines 31 and 32,"hydro-carylene" should read -hydro-carbylene-.

Signed and sealed this 1st day of April 1975.

Attest:

R' TEI C. 22x80? Commissioner of Patents fittest-tin; Officer andTrademarks

1. A CONCENTRATE COMPRISING (A) FROM 50 TO 98 WEIGHT PERCENT OF ANOLEOPHILIC ORGANIC SULFUR COMPOUND OR MIXTURE THEREOF CONTAINING FROM 3TO 40 WEIGHT PERCENT SULFUR AND SELECTED FROM THE GROUP CONSISTING OFSULFURIZED ESTERS, SULFURIZED TERPENES, SULFURIZED OLEFINS, AROMATICSULFIDES, ALKYL SULFIDES, AMIDO-SUBSTITUTED DITHIAZOLE-THIONES,SULFURIZED HYDROXY ESTERS, POLYALKYLPHENOL SULFIDES AND SULFURIZEDALKALINE EARTH METAL PHENATES, (B) FROM 1 TO 20 WEIGHT PERCENT OF ABISPHOSPHORAMIDE PREPARED BY CONTACTING WITHIN A LIQUID PHASE REACTIONMEDIUM (1) PHOSPHORUS OXYCHLORIDE (2) A DIFUNCTIONAL COMPOUND HAVING THESTRUCTURE:
 2. from 0.05 to 5 weight percEnt of a bisphosphoramide havingthe formula:
 2. The composition defined in claim 1 wherein saiddifunctional compound is seLected from piperazine,methylene-dipiperazine, dimethylenepiperazine andtrimethylenedipiperazine.
 3. The composition defined in claim 1 whereinsaid oleophilic organic sulfur compound is selected from the groupconsisting of sulfurized C1 to C20 alkyl esters of C8 to C24 fattyacids, sulfurized C8 to C30 unsaturated aliphatic hydrocarbons, C10 toC30 sulfurized hydroxyesters, polyalkylphenol sulfides, and sulfurizedmetal phenates.
 4. The composition defined in claim 3 wherein saidbisphosphoramide is the reaction product of dicocomaine with piperazineand phosphorus oxychloride.
 5. A lubricating composition comprising (1 )a major amount of an oil of lubricating viscosity, (2 ) from 0.5 to 10weight percent of an oleophilic organic sulfur compound or mixturethereof containing from 3 to 40 weight percent sulfur and selected fromthe group consisting of sulfurized esters, sulfurized terpenes,sulfurized olefins, aromatic sulfides, alkyl sulfides, amido-substituteddithiazole-thiones, sulfurized hydroxy esters, polyalkylphenol sulfidesand sulfurized alkaline earth metal phenates, and (3 ) from about 0.05to 5 weight percent of a bisphosphoramide prepared by reacting (a)phosphorus oxychloride (b) a difunctional compound of the formula: 6.The composition defined in claim 5 wherein said X is nitrogen, said Y isnitrogen and said R2 is a hydrocarylene.
 7. The composition defined inclaim 5 wherein said difunctional compound is selected from piperazine,methylene dipiperazine, dimethylene piperazine and trimethylenedipiperazine.
 8. The composition defined in claim 5 wherein said oil oflubricating viscosity is present in major amounts, said organic sulfurcompound is present at a concentration of 1 to 6 weight percent and saidbisphosphoramide is present at a concentration of 0.1 to 1 weightpercent.
 9. The composition defined in claim 5 wherein said organicsulfur compound is a sulfurized C1 to C20 alkyl ester of an unsaturatedC8 to C24 fatty acid.
 10. The composition defined in claim 9 whereinsaid oil has a viscosity of 50 to 5000 SUS at a temperature of 100*F.11. A composition of matter comprising a major portion of an oil oflubricating viscosity containing